Baeyer-Villiger oxidation and oxidative cascade reactions with aqueous hydrogen peroxide catalyzed by lipophilic Li[B(C6F5)4] and Ca[B(C6F5)4]2.

Angew Chem Int Ed Engl. 2012 Sep 3;51(36):9093-6.

Uyanik M, Nakashima D, Ishihara K.

Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya, Japan.

 

Abstract

 

Efficient and selective: Two lipophilic catalysts were used for Baeyer-Villiger (BV) oxidations to give lactones in high yields. Cascade reactions involving this BV oxidation were used to selectively obtain either unsaturated carboxylic acids or hydroxylactones in high yields from {Beta}-silyl cyclohexanones.

Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

 

 

Go To Journal

 

AdditionalInformation

The Baeyer–Villiger (BV) oxidation of ketones and aldehydes to the corresponding esters or lactones is one of the most important transformations.  Recently, Ishihara et al. succeeded in LiB(C₆F₅)₄– or Ca[B(C₆F₅)₄]₂-catalyzed BV oxidation with aqueous hydrogen peroxide.  These liphophilic catalysts were very effective for the use of aqueous hydrogen peroxide (Scheme 1).  The catalytic co-use of oxalic acid further accelerated the BV oxidation.

 

 

 

3-Trimethylsilylcycloalkanones could be oxidized to either the corresponding unsaturated carboxylic acids or hydroxylactones in high yield through BV oxidation/-elimination reaction sequences and the subsequent epoxidation/cyclization reaction sequences, by controlling the amounts of H₂O₂ and oxalic acids.

 

 

 

 

References

Uyanik, M.; Ishihara, K. ACS Catal. 2013, 3, 513.

Uyanik, M.; Nakashima, D.; Ishihara, K. Angew. Chem. Int. Ed. 2012, 51, 9093.